Catalyst system and its use in olefin polymerization

ABSTRACT

A polymerization catalyst system and a method for preparing the catalyst system is disclosed. The catalyst system includes a bulky ligand metallocene catalyst compound, preferably containing a single cyclopentadienyl or substituted cyclopentadienyl-type ring system, a Group  13  element containing first modifier, and a cycloalkadiene second modifier. The present invention also provides a process for polymerizing olefin(s) utilizing the catalyst systems described herein.

RELATED APPLICATION DATA

[0001] The present application is a divisional of U.S. patentapplication Ser. No. 09/714,371, filed Nov. 16, 2000, now issued as U.S.Pat. No. ______.

FIELD OF THE INVENTION

[0002] The present invention relates generally to the field of bulkyligand metallocene catalysts and their use for olefin(s) polymerization.In particular, the invention is directed to a catalyst system withenhanced activity, which includes a bulky ligand metallocene catalystcompound and a method for preparing such a system. More specifically,the present invention is directed to a catalyst system comprising abulky ligand metallocene catalyst compound, an activator compound, aGroup 13 element containing first modifier, and a cycloalkadiene secondmodifier, to a method of preparing such a catalyst system, and for itsuse in the polymerization of olefin(s).

BACKGROUND OF THE INVENTION

[0003] Numerous catalysts and catalyst systems have been developed thatprovide polyolefins with certain advantageous properties. One class ofthese catalysts are now commonly referred to as metallocenes.Metallocenes are broadly defined as organometallic coordinationcomplexes containing one or more moieties in association with a metalatom from Groups 3 to 17 or the Lanthanide series of the Periodic Tableof Elements. These catalysts are highly useful in the preparation ofpolyolefins, allowing one to closely tailor the final properties of apolymer.

[0004] Although metallocene catalysts are used extensively to obtainpolyolefins with molecular weight, polydispersity, melt index, and otherproperties well suited for a desired application, the use of thesecatalysts is expensive. It is therefore an object of this invention toincrease the activity of metallocene catalyst systems and thereby reducethe cost associated with utilizing such a system.

[0005] Organoborate and boron compounds are known as activators forolefin polymerization systems. The use of these compounds as activators,instead of alumoxane compounds, to form active olefin polymerizationcatalysts is documented in the literature. Marks (Marks et al. 1991)reported such a transformation for olefin polymerization using Group 4metallocene catalysts containing alkyl leaving groups activated withtris(pentafluorophenyl)borane. Similarly, Chien et al. (1991) activateda dimethyl zirconium catalyst with tetra(pentafluorophenyl)borate.However, when Chien used methylalumoxane (MAO) as well as the borate forthe activation of the dimethyl zirconium catalyst for the polymerizationof propylene, only a small amount of polymer was produced.

[0006] U.S. Pat. No. 5,747,406 discloses an increased catalytic activitywhen using indene or other cycloalkadienes with a half-sandwichtransition metal catalyst and MAO as the activating activator. Thiscatalyst composition demonstrates enhanced activity in thepolymerization of olefins. For the polymerization of ethylene/1-hexeneusing indenyl zirconium tris(diethyl-carbamate), modified MAO andindene, the addition of indene increased the activity of the system 3.5times.

[0007] In spite of the advances in the prior art, there exists a need toprovide for a highly active metallocene catalyst systems, for a methodfor its preparation and use in the polymerization of olefin(s).

SUMMARY OF THE INVENTION

[0008] The present invention provides a catalyst system and a method forpreparing a catalyst system which includes a bulky ligand metallocenecatalyst compound, an activator compound, a Group 13 element containingfirst modifier, and a cycloalkadiene second modifier. The first andsecond modifiers, when utilized together, act to enhance the activity ofthe catalyst system. The present invention also provides a process forpolymerizing olefin(s) utilizing the catalyst systems described herein.

DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention provides a metallocene catalyst systemhaving enhanced activity, a method for preparing this catalyst systemand a method for polymerizing olefin(s) utilizing same. Morespecifically, the present invention provides for a catalyst system whichincludes a bulky ligand metallocene catalyst compound, preferably a halfsandwich bulky ligand metallocene catalyst compound, an activatorcompound, a Group 13 element containing first modifier, and acycloalkyldiene second modifier.

[0010] Bulky Ligand Metallocene Compounds

[0011] The catalyst system of the invention includes a bulky ligandmetallocene catalyst. Bulky ligand metallocene compounds generallyinclude both half and full sandwich compounds having one or more bulkyligands bonded to at least one metal atom. Typical bulky ligandmetallocene compounds are generally described as containing one or morebulky ligand(s) and one or more leaving group(s) bonded to at least onemetal atom. The bulky ligand metallocene compounds preferred include oneunsubstituted or substituted, cyclopentadienyl ligand orcyclopentadienyl-type ligand. These types of bulky ligand metallocenecompounds are also referred to as half-sandwich compounds ormono-cyclopentadienyl compounds (mono-Cps), and the terms are usedinterchangeably herein.

[0012] The unsubstituted or substituted, cyclopentadienyl ligand orcyclopentadienyl-type bulky ligand, is generally represented by one ormore open, acyclic, or fused ring or ring system typically composed ofatoms selected from Groups 13 to 16 atoms of the Periodic Table ofElements. Preferably the atoms are selected from the group consisting ofcarbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boronand aluminum or a combination thereof. The unsubstituted or substituted,cyclopentadienyl ligands or cyclopentadienyl-type ligands includeheteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands.

[0013] Non-limiting examples of these bulky ligands includecyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenylligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenylligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands,azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands,phosphinimine (WO 99/40125), pyrrolyl ligands, pyrozolyl ligands,carbazolyl ligands, borabenzene ligands and the like, includinghydrogenated versions thereof, for example tetrahydroindenyl ligands.

[0014] Bulky ligands which comprise one or more heteroatoms includethose ligands containing nitrogen, silicon, boron, germanium, sulfur andphosphorous, in combination with carbon atoms to form an open, acyclic,or preferably a fused, ring or ring system, such as, for example, aheterocyclopentadienyl ancillary ligand. Other bulky ligands include butare not limited to bulky amides, phosphides, alkoxides, aryloxides,imides, carbolides, borollides, porphyrins, phthalocyanines, corrins andother polyazomacrocycles.

[0015] The cyclopentadienyl ligand or cyclopentadienyl-type bulky ligandmay be unsubstituted or substituted with a combination of substituentgroups R. Non-limiting examples of substituent groups R include one ormore from the group selected from hydrogen, or linear, branched alkylradicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals oraryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0016] The metal atom is preferably selected from Groups 3 through 15and the lanthanide or actinide series of the Periodic Table of Elements.Preferably the metal is a transition metal from Groups 4 through 12,more preferably Groups 4, 5 and 6, even more preferably the transitionmetal is from Group 4 and most preferably titanium, zirconium orhafnium.

[0017] In one embodiment, the half-sandwich or mono-Cp bulky ligandcatalyst compounds utilized in the catalyst system of the invention isrepresented by Formula I as set forth below:

LMX_(n)  Formula I

[0018] wherein:

[0019] M is a metal atom from Groups 3 to 15 or the Lanthanide series ofthe Periodic Table of Elements, preferably Groups 4, 5 and 6, even morepreferably Group 4 and most preferably Ti, Zr or Hf;

[0020] L is a substituted or unsubstituted, 7r-bonded bulky ligandcoordinated to M, preferably a substituted or unsubstitutedcyclopentadienyl or cyclopentadienyl-type ligand;

[0021] each X is independently hydrogen, an aryl, alkyl, alkenyl,alkylaryl, or arylalkyl radical having 1 to 20 carbon atoms, ahydrocarboxy radical having 1 to 20 carbon atoms, a halide, a nitrogencontaining radical having 1 to 20 carbon atoms; and wherein

[0022] the value of n depends upon the valence state of M and ispreferably 2, 3 or 4.

[0023] In another embodiment, the half-sandwich or mono-Cp bulky ligandcatalyst compounds utilized in the catalyst system of the invention isrepresented by Formula II or Formula III as set forth below:

[0024] wherein:

[0025] M is a metal atom from Groups 3 to 15 or the Lanthanide series ofthe Periodic Table of Elements, preferably Groups 4, 5 and 6, even morepreferably Group 4 and most preferably Ti, Zr or Hf;

[0026] L is a substituted or unsubstituted, π-bonded bulky ligandcoordinated to M, preferably a substituted or unsubstitutedcyclopentadienyl or cyclopentadienyl-type ligand;

[0027] Q can be the same or different and is independently selected fromthe group consisting of —O—, —NR—, —CR₂ and —S—;

[0028] Y is either C or S;

[0029] Z is selected from the group consisting of —OR, —NR₂, —CR₃, —SR,—SiR₃, —PR₂, —H, and substituted or unsubstituted aryl group with theproviso that when Q is —NR— then Z is selected from the group consistingof —OR, —NR₂, —SR, —SiR₃, —PR₂ and —H;

[0030] n is 1 or 2;

[0031] A is a univalent anionic group when n is 2 or A is a divalentanionic group when n is 1; when n is 2, A can be the group formed byQQYZ depicted in formula I above; and

[0032] As used above, each R can be the same or different and isindependently a group containing carbon, silicon, nitrogen, oxygen,and/or phosphorus where one or more R groups may be attached to the Lsubstituent, preferably R is a hydrocarbon group containing from 1 to 20carbon atoms, most preferably an alkyl, cycloalkyl or an aryl group; and

[0033] wherein:

[0034] M is a metal atom from Groups 3 to 15 or the Lanthanide series ofthe Periodic Table of Elements, preferably Groups 4, 5 and 6, even morepreferably Group 4 and most preferably Ti, Zr or Hf;

[0035] L is a substituted or unsubstituted, π-bonded bulky ligandcoordinated to M, preferably a substituted or unsubstitutedcyclopentadienyl or cyclopentadienyl-type ligand;

[0036] Q can be the same or different and is independently selected fromthe group consisting of —O—, —NR—, —CR₂— and —S—

[0037] Y is either C or S;

[0038] Z is selected from the group consisting of —OR, —NR₂, —CR₃, —SR,—SiR₃, —PR₂, —H, and substituted or unsubstituted aryl group with theproviso that when Q is —NR— then Z is selected from the group consistingof —OR, —NR₂, —SR, —SiR₃, —PR₂ and —H;

[0039] n is 1 or 2;

[0040] A is a univalent anionic group when n is 2 or A is a divalentanionic group when n is 1; when n is 2, A can be the group formed byQQYZ depicted in formula II above;

[0041] R can be the same or different and is independently a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus whereone or more R groups may be attached to the L substituent, preferably Ris a hydrocarbon group containing from 1 to 20 carbon atoms, mostpreferably an alkyl, cycloalkyl or an aryl group;

[0042] T is a bridging group selected from the group consisting of analkylene or arylene group containing from 1 to 10 carbon atomsoptionally substituted with carbon or heteroatoms, germaniun, siliconeand alkyl phosphine; and

[0043] m is 1 to 7, preferably 2 to 6, most preferably 2 or 3.

[0044] In Formula II and III above, the substituent formed by Q, Q, Yand Z is preferably a unicharged polydentate ligand exerting electroniceffects due to its high polarizibility, similar to the cyclopentadienylgroup (L) described above. In preferred embodiments of this invention,the disubstituted carbamates, shown in Formula IV,

[0045] and the carboxylates, shown in Formula V,

[0046] are employed.

[0047] Illustrative examples of these mono-Cp bulky ligand metallocenecatalyst compounds are which may be utilized in the catalyst system ofthe invention include: indenyl zirconium tris(pivalate), indenylzirconium tris(p-toluate), indenyl zirconium tris(benzoate),(1-methylindenyl) zirconium tris(pivalate), (2-meth-ylindenyl) zirconiumtris(diethylcarbamate), (methylcyclopentadienyl) zirconiumtris(pivalate), (cyclopentadienyl) zirconium tris(pivalate),(pentamethylcyclopentadienyl) zirconium tris(benzoate),n-butylcyclopentadienylzirconium trispivalate,(n-butylcyclopenta-dienyl)tris-(benzoate), (tetrahydroindenyl)zirconiumtris(pivalate), (tetrahydroindenyl)-zirconium tris(benzoate),(tetrahydroindenyl)zirconium tris(pentenate),(1,3-dimethylcyclopentadienyl)zirconium tris(pivalate),(1,3-methylethyl-cyclopentadienyl)zirconium tris(pivalate),tetramethylcyclopentadienyl)zirconium tris(pivalate),(pentamethylcyclopentadienyl)zirconium tris(pivalate),(cyclopenty-lcyclopentadienyl)zirconium tris(benzoate),(benzylcyclopentadienyl)zirconium tris(benzoate),(n-butylcyclopentadienyl)hafnium tris(pivalate),(n-butylcyclopentadienyl)titanium tris(pivalate).pentamethylcyclopentadienyltitanium isopropoxide,pentamethylcyclopentadienyltribenzyl titanium,dimethylsilyltetramethylcyclopentadienyl-tert-butylamido titaniumdichloride, pentamethylcyclopentadienyl titanium trimethyl,dimethylsilyltetramethyl-cyclopentadienyl-tert-butylamido zirconiumdimethyl, dimethylsilyltetramethyl-cyclopentadienyl-dodecylamido hafniumdihydride and dimethylsilyltetramethyl-cyclopentadienyl-dodecylamidohafnium dimethyl. Particularly preferred mono-Cp compounds utilized are1,3-dimethylcyclopentadienylzirconium trispivalate and indenylzirconiumtrispivalate.

[0048] The above mono-Cp bulky ligand metallocene catalyst compounds maybe made using any conventional process as is well known. In one methodof manufacturing this catalyst, a source of cyclopentadienyl-type ligandis reacted with a metal compound of the formula M(CR₂)₄ or M(NR₂)₄ inwhich M and R are defined above. The resulting product is then dissolvedin an inert solvent, such as toluene, and the heterocummulene such asCO₂, is contacted with the dissolved product to insert into one or moreM-CR₂ or M-NR₂ bonds to form, in this instance, a carboxylate or acarbamate. In another method of manufacturing this catalyst is describedin WO 00/10709, published Jan. 13, 2000, and incorporated herein byreference.

[0049] Activator Compounds

[0050] The above described polymerization catalyst compounds aretypically activated in various ways to yield compounds having a vacantcoordination site that will coordinate, insert, and polymerizeolefin(s). The catalyst system of the invention may include a singleactivator compound or a combination of activator compounds. For thepurposes of this patent specification and appended claims, the term“activator” is defined to be any compound or component or method whichcan convert a neutral bulky ligand metallocene catalyst compound to acatalytically active bulky ligand metallocene catalyst cation.

[0051] In one embodiment, the catalyst system of the invention includesan alumoxane as an activator. Alumoxane activators are generallyoligomeric compounds containing —Al(R)—O— subunits, where R is an alkylgroup. Examples of alumoxanes include methylalumoxane (MAO), modifiedmethylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alumoxanesmay be produced by the hydrolysis of the respective trialkylaluminumcompound. MMAO may be produced by the hydrolysis of trimethylaluminumand a higher trialkylaluminum such as triisobutylaluminum and aregenerally more soluble in aliphatic solvents and more stable duringstorage. There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. No. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199,5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815,5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793,5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177,5,854,166, 5,856,256 and 5,939,346 and European publications EP-A-0 561476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCTpublication WO 94/10180, all of which are herein fully incorporated byreference.

[0052] In another embodiment the catalyst system of the inventionincludes modified methyl alumoxane in heptane (MMAO3A) commerciallyavailable from Akzo Chemicals, Inc., Holland, under the trade nameModified Methylalumoxane type 3A.

[0053] In another embodiment, organoaluminum compounds are utilized asactivators. Non limiting examples of suitable organoaluminum activatorcompounds include trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike.

[0054] In another embodiment, other suitable activators which may beutilized are disclosed in WO 98/09996, incorporated herein by reference,which describes activating bulky ligand metallocene-type catalystcompounds with perchlorates, periodates and iodates including theirhydrates. WO 98/30602 and WO 98/30603, incorporated by reference,describe the use of lithium (2,2′-bisphenyl-ditrimethylsilicate).4THF asan activator for a bulky ligand metallocene catalyst compound.

[0055] In another embodiments, the catalyst system of the invention mayinclude activators such as those disclosed in WO 99/18135, whichdescribes the use of organo-boron-aluminum acitivators, EP-B1-0 781 299which describes using a silylium salt in combination with anon-coordinating compatible anion, both incorporated herein byreference. Additional methods of activation such as using radiation (seeEP-B 1-0 615 981 herein incorporated by reference), electrochemicaloxidation, and the like are also contemplated as activating methods forthe purposes of rendering the neutral bulky ligand metallocene catalystcompound or precursor to a bulky ligand metallocene cation capable ofpolymerizing olefins. Other activators or methods for activating a bulkyligand metallocene-type catalyst compound are described in for example,U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO99/42467 (dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are herein incorporated by reference. Stillother activators include those described in PCT publication WO 98/07515such as tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate, alsoincorporated herein by reference. Combinations of activators are alsocontemplated by the invention, please see for example, EP-B1 0 573 120,PCT publications WO 94/07928 and WO 95/14044 and U.S. Pat. Nos.5,153,157 and 5,453,410 all of which are fully incorporated herein byreference.

[0056] Modifiers for the Catalyst System

[0057] The catalyst system of the present invention also includes aGroup 13 element containing first modifier and a cycloalkadienyl secondmodifier which, when utilized together, act to enhance the activity ofthe catalyst system.

[0058] Group 13 Element Containing First Modifier

[0059] In one embodiment, the first modifier is utilized in the catalystsystem of the present invention includes a cation and an anioncomponent, and is represented by Formula VI below:

(L′-H)_(d) ⁺(A^(d−))   Formula VI

[0060] wherein L′ is an neutral Lewis base;

[0061] H is hydrogen;

[0062] (L′-H)⁺is a Bronsted acid

[0063] A^(d−) is a non-coordinating anion having the charge d−

[0064] d is an integer from 1 to 3.

[0065] The cation component, (L-H)_(d) ⁺ may include Bronsted acids suchas protons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an akyl or aryl, from thebulky ligand metallocene catalyst compound, resulting in a cationictransition metal species.

[0066] In one embodiment the cation component (L-H)_(d) ⁺ includesammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof,preferably ammoniums of methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniumsfrom triethylphosphine, triphenylphosphine, and diphenylphosphine,oxomiuns from ethers such as dimethyl ether diethyl ether,tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethylthioethers and tetrahydrothiophene and mixtures thereof. In a preferredembodiment, the cation component (L-H)_(d) ⁺ of the first modifier isdimethylanaline.

[0067] In another embodiment cation component (L-H)_(d) ⁺ may also be anabstracting moiety such as silver, carboniums, tropylium, carbeniums,ferroceniums and mixtures, preferably carboniums and ferroceniums. In apreferred embodiment, the cation component (L-H)_(d) ⁺ of the firstmodifier is triphenyl carbonium.

[0068] In another embodiment, the anion component A_(d) ⁻ of the firstmodifier includes those anions having the formula [M^(k+)Q_(n)]^(d−)wherein k is an integer from 1 to 3; n is an integer from 2 to 6; n−k=d;M is an element selected from Group 13 of the Periodic Table of theElements and Q is independently a hydride, bridged or unbridgeddialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, andhalosubstituted-hydrocarbyl radicals, with Q having up to 20 carbonatoms with the proviso that in not more than 1 occurrence is Q a halide.In a preferred embodiment, each Q is a fluorinated hydrocarbyl grouphaving 1 to 20 carbon atoms, more preferably each Q is a fluorinatedaryl group, and most preferably each Q is a pentafluoryl aryl group.

[0069] In another embodiment, the anion component A^(d−) of the firstmodifier may also include diboron compounds as disclosed in U.S. Pat.No. 5,447,895, which is fully incorporated herein by reference.

[0070] In another embodiment the first modifier is a tri-substitutedboron, tellurium, aluminum, gallium, or indium compound or mixturesthereof. The three substituent groups are each independently selectedfrom alkyls, alkenyls, halogen, substituted alkyls, aryls arylhalides,alkoxy and halides. Preferably, the three groups are independentlyselected from halogen, mono or multicyclic (including halosubstituted)aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred arealkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groupshaving 3 to 20 carbon atoms (including substituted aryls). In anotherembodiment, the three groups are alkyls having 1 to 4 carbon groups,phenyl, napthyl or mixtures thereof. In another embodiment each of thethree substituent groups is a fluorinated hydrocarbyl group having 1 to20 carbon atoms, preferably a fluorinated aryl group, and morepreferably a pentafluoryl aryl group. In another embodiment the firstmodifier is trisperfluorophenyl boron or trisperfluoronapthyl boron.

[0071] In another embodiment the first modifier or activity promoter isan organometallic compound such as the Group 13 organometallic compoundsof U.S. Pat. Nos. 5,198,401, 5,278,119, 5,407,884, 5,599,761 5,153,157,5,241,025, and WO-A-93/14132, WO-A-94/07927, and WO-A-95/07941, alldocuments are incorporated herein by reference.

[0072] In another embodiment, the first modifier is selected fromtris(pentafluorophenyl)borane (BF-15), dimethylaniliniumtetra(pentafluorophenyl)borate (BF-20), dimethylaniliniumtetra(pentafluorophenyl)aluminate, dimethylaniliniumtetrafluoroaluminate, tri(n-butyl)ammonium)tetra(pentafluorophenyl)borate, tri(n-butyl)ammonium)tetra(pentafluorophenyl)-aluminate, tri(n-butyl)ammonium)tetrafluoroaluminate, the sodium, potassium, lithium, tropyliun and thetriphenylcarbenium salts of these compounds, or from combinationsthereof. In preferred embodiment, the first modifier isN,N-dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbeniumtetra(perfluorophenyl)borate.

[0073] Cycloalkadienyl Second Modifier

[0074] The use of a second modifier in combination with first modifiersin the catalyst system of the invention significantly enhances thecatalyst system's activity.

[0075] In one embodiment, the second modifier or activity promotorutilized in the catalyst system a cycloalkadiene compound. Acycloalkadiene is an organocyclic compound having two or more conjugateddouble bonds, examples of which include cyclic hydrocarbon compoundshaving 2 to 4 conjugated double bonds and 4 to 24, preferably 4 to 12,carbons atoms. The cycloalkadiene may optionally be substituted with agroup such as alkyl or aryl of 1 to 12 carbon atoms.

[0076] Examples of activity enhancing cycloalkadienes includeunsubstituted and substituted cyclopentadienes, indenes, fluorenes, andfulvenes, such as cyclopentadiene, methylcyclopentadiene,ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene,octylcyclopentadiene, 1,2-dimethylcyclopentadiene,1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene,1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene,4-methyl-1-indene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene,fluorene, methylfluorene, cycloheptatriene, methylcycloheptatriene,cyclooctatraene, methylcyclooctatraene, fulvene and dimethylfulvene.These compounds may be bonded through an alkylene group of 2-8,preferably 2-3, carbon atoms, such as for example bis-indenylethane,bis(4,5,6,7-tetrahydro-1-indenyl)ethane,1,3-propanedinyl-bis(4,5,6,7-tetrahydro)indene, propylene-bis(1-indene),isopropyl(1-indenyl) cyclopentadiene, diphenylmethylene(9-fluorenyl),cyclopentadiene and isopropylcyclopentadienyl-1-fluorene. Preferredcycloalkydienes are the 1,3-type dienes such cyclopentadiene and indene.

[0077] In the catalyst system of this invention, the addition of thefirst and second modifiers, described above, have been found to have asynergistic effect on the catalytic activity of a bulky ligandmetallocene mono-Cp/MAO catalyst component. When the first modifier, forexample BF-20, is used alone, no enhancement of the polymerizationactivity occurs, and when the second modifier, for example indene, isused alone as a modifier the enhancement is not as significant as whenboth are utilized together. It is therefore an aspect of the presentinvention that the activity of the catalyst system for thepolymerization of olefins is enhanced relative to the activity of thesame catalyst system without the addition of the Group 13 elementcontaining and the cycloalkadiene modifiers. In one embodiment of theinvention, the activity of the catalyst system is increased at least200%, more preferably at least 400%, more preferably 600%, morepreferably at least 700%, more preferably at least 800%, more preferablyat least 900%, or more preferably at least 1000% relative to theactivity of the same catalyst system to which no modifier has beenadded.

[0078] In one embodiment, each of the modifiers are added in an amountnecessary to effect an increase in the catalyst systems activity. Inanother embodiment, the molar ratio of the Group 13 element containingfirst modifier to the metal contained in the bulky ligand metallocenecatalyst compound is about 0.01 to 100, preferably about 0.01 to 10,more preferably 0.05 to 5 and even more preferably 0.1 to 2.0. Inanother embodiment, the molar ratio of the cycloalkadiene secondmodifier to the metal contained in the bulky ligand metallocene catalystcompound is about 0.01 to 100, preferably about 0.01 to 10, morepreferably about 0.05 to 5, and even more preferably 0.1 to 2.0.

[0079] Polymerization Process

[0080] The catalyst system of the invention described above is suitablefor use in any polymerization process over a wide range of temperaturesand pressures. The temperatures may be in the range of from −60° C. toabout 280° C., preferably from 50° C. to about 200° C., and thepressures employed may be in the range from 1 atmosphere to about 500atmospheres or higher.

[0081] Polymerization processes include solution, gas phase, slurryphase and a high pressure process or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefins at least one of which is ethylene or propylene.

[0082] In one embodiment, the process of this invention is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. Polyolefins that can be produced using these catalyst systemsinclude, but are not limited to, homopolymers, copolymers andterpolymers of ethylene and higher alpha-olefins containing 3 to about12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, and 1-octene, with densities ranging from about 0.86to about 0.97; polypropylene; ethylene/propylene rubbers (EPR's);ethylene/propylene/diene terpolymers (EPDM's); and the like.

[0083] Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

[0084] In the most preferred embodiment of the process of the invention,a copolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

[0085] Typically in a gas phase polymerization process a continuouscycle is employed wherein one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228, all of which are fully incorporated herein byreference.)

[0086] The reactor pressure in a gas phase process may vary from about60 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0087] The reactor temperature in a gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 11 0° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0088] Other gas phase processes contemplated by the process of theinvention include series or multistage polymerization processes. Alsogas phase processes contemplated by the invention include thosedescribed in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, andEuropean publications EP-A-0 794 200 EP-B 1-0 649 992, EP-A-0 802 202and EP-B-634 421 all of which are herein fully incorporated byreference.

[0089] In a preferred embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0090] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0091] A preferred polymerization technique of the invention is referredto as a particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

[0092] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0093] Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555, which are fullyincorporated herein by reference

[0094] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the presence ofa bulky ligand metallocene catalyst system of the invention and in theabsence of or essentially free of any scavengers, such astriethylaluminum, trimethylaluminum, tri-isobutylaluminum andtri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and thelike. This preferred process is described in PCT publication WO 96/08520and U.S. Pat. No. 5,712,352 and 5,763,543, which are herein fullyincorporated by reference.

[0095] Polymer Products

[0096] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymersproduced by the process of the invention include linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, lowdensity polyethylenes, polypropylene and polypropylene or polyethylenecopolymers.

[0097] The polymers of the invention may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes produced via conventional Ziegler-Nattaand/or bulky ligand metallocene catalysis, elastomers, plastomers, highpressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

[0098] The preferred polymers of this invention contain at least 50%polyethylene. Comonomers such as 1-butene, 1-pentane, 1-hexane,benzylcyclobutante and styrene are preferred. The preferred polymerproduct will have a density of from 0.85 to 0.96 g/cc, more preferablyfrom about 0.88 to 0.96 g/cc and most preferably from about 0.90 to 0.96g/cc.

[0099] Polymers produced by the process of the invention and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, geomembranes,and pond liners. Molded articles include single and multi-layeredconstructions in the form of bottles, tanks, large hollow articles,rigid food containers and toys, etc.

Examples

[0100] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

[0101] The Activity values, shown in Table 1, are normalized valuesbased upon grams of polymer produced per mmol of transition metal in thecatalyst per hour per 100 psi (689 KPa) of ethylene polymerizationpressure.

[0102] 1H NMR spectra were measured by a Bruker AMX 300

[0103] Polydispersity Index (PDI) is equivalent to Molecular WeightDistribution (Mw/Mn, where Mw is weight average molecular weight and Mnis number average molecular weight), as determined by gel permeationchromatography.

[0104] Methylalumoxane (MAO) was used in toluene (30 wt %). (BF-20) isdimethylanilinium tetra(pentafluorophenyl)borate (BF-20). CatalystComponent A is 1,3-dimethylcyclopentadienylzirconium trispivalate andCatalyst Component B is indenylzirconium trispivalate.

Example 1 Synthesis of (1,3-Dimethylcyclopentadienyl)zirconiumtrispivalate (Catalyst Component A)

[0105] To a solution of bis(1,3-dimethylcyclopentadienyl)zirconiumdichloride (1.390 g, 3.99 mmol) and pivalic acid (1.520 g, 14.9 mmol) intoluene at 25° C. was added neat triethylamine (1.815 g, 18.10 mmol)with stirring. A white precipitate formed immediately which was removedby filtration. The compound was isolated as a pale-yellow powder in 88%yield and exhibited purity above 99% based on NMR results. ¹H NMR(toluene-d₈): 65.84 (m, 2H), 5.53 (m, 1H), 2.18 (s, 6H), 1.13 (s, 27H).

Example 2 Preparation of Indenylzirconium Trispivalate (CatalystComponent B)

[0106] The compound (Ind)Zr(NEt₂)₃ (37 mg, 0.088 mmole) was dissolved in1.0 mL of benzene-d6. A solution of pivalic acid (27 mg, 0.26 mmole) in1.0 mL benzene-d6 was added with stirring. ¹H NMR exhibited resonancesassigned to NEt₂H and (Ind)Zr(O₂ CCMe₃)₃. ¹H NMR (C₆ D₆) d 7.41 (AA′BB′,indenyl, 2H), 6.95 (AA′BB′, indenyl, 2H), 6.74 (t, J=3.3 Hz, 2-indenyl,1H), 6.39 (d, J=3.3 Hz, 1-indenyl, 2H), 1.10 (s, CH₃, 27H).

Example 3 Polymerization Process

[0107] Utilizing the catalyst compounds prepared in Examples 1 and 2,polyethylene was produced in a slurry phase reactor.

[0108] For each of Component A and B prepared in Examples 1 and 2, asolution in toluene (0.0036M) was prepared. An aliquot (0.5 ml) of thissolution was added to a 6 ounce (177 ml) bottle containing an aliquot(0.2 ml) of MAO in toluene (3.15M). An aliquot (0.6 ml) of indene intoluene (0.0030M) then an aliquot (1.0 ml) of BF-20 in toluene (0.0018M) was added to the mixing bottle. Anhydrous conditions weremaintained. The polymerization time for all the Examples 1 and 2 was 30minutes. Table 1 below shows the catalyst composition makeup forExamples 1 and 2.

[0109] The slurry reactor was a 1.65 liter, stainless steel autoclaveequipped with a mechanical agitator. The reactor was first dried byheating at 96° C. under a stream of dry nitrogen for 40 minutes. Aftercooling the reactor to 5 0° C., 1000 ml of hexane was added and thereactor components were stirred under a gentle flow of nitrogen.Hexene-1 (20 ml) was added to the reactor as well as an aliquot oftriisobutylaluminum in hexane (0.5 ml, 0.86M) to act as a scavenger. Thetemperature of the reactor was gradually raised to 70° C. and thereactor was pressured to 150 psi (1034 KPa) with ethylene. The pre-mixedcatalyst solution prepared above was then injected into the reactor tostart the polymerization. Heating was continued until a polymerizationtemperature of 85° C. was attained. Unless otherwise noted,polymerization was continued for 30 minutes, during which time ethylenewas continually added to the reactor to maintain a constant pressure. Atthe end of 30 minutes, the reactor was vented and opened.

[0110] Comparative Example 4-Comparative Runs C1-C6

[0111] In Comparative Runs C1 to C6, polyethylene was produced underconditions similar to those of Examples 1 and 2 with the exception thatthe mixture of indene and BF-20 was not used. The polymerization timefor each run in Example 4 was 30 minutes.

[0112] The catalyst system activity, the molecular weights (Mw and Mn),the molecular weight distributions (Mw/Mn, also known as PDI) of variouspolyethylene made in from the catalyst compounds prepared in theExamples shown in Table 1. As shown in Table 1, the catalyst systems ofthe invention comprising the Group 13 element containing first modifierand the cycloalkadiene second modifier possessed significantly higheractivity. TABLE 1 Example or Indene/Zr BF-20/Zr 1(MAO)/Zr run Catalystmolar ratio molar ratio molar ratio Activity Mw Mn PDI C1 A — — 42015058 427424 123358 3.5 C2 A — 1.0 420 14431 395835 142874 2.8 C3 A 1.0— 420 66525 364033 122111 3  1 A 1.0 1.0 420 200296 222391 54609 4.1 C4B — — 420 12549 290792 90980 3.2 C5 B — 1.0 420 14379 295051 102456 2.9C6 B 1.0 — 420 28078 412101 166874 2.5  2 B 1.0 1.0 420 99921 20715158686 3.5

We claim:
 1. A catalyst system for polymerizing olefin(s) comprising a)a bulky ligand metallocene catalyst compound; b) a first modifiercomprising a Group 13 element containing compound; and c) a secondmodifier comprising a cycloalkyldiene.
 2. The catalyst system of claim 1wherein the first modifier may be represented by: (L′-H)_(d) ⁺(A^(d−))wherein L′ is an neutral Lewis base; H is hydrogen; (L′-H)⁺ is aBronsted acid; A^(d−) is a non-coordinating anion having the charge d−;and d is an integer from 1 to
 3. 3. The catalyst system of claim 2wherein (L-H)_(d) ⁺ is selected from the group consisting of ammoniumsof methylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene andcobinations thereof.
 4. The catalyst system of claim 2 wherein (L-H)d+isselected from the group consisting of ammoniums of methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine,pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, andcombinations thereof.
 5. The process of claim 2 wherein A^(d−) may berepresented by the formula [M^(k+)Q_(n)]^(d−)wherein k is an integerfrom 1 to 3; n is an integer from 2 to 6; n−k=d; M is an elementselected from Group 13 of the Periodic Table of the Elements and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, with Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide.
 6. The process of claim 5 wherein each Q is afluorinated hydrocarbyl group having 1 to 20 carbon atoms.
 7. Thecatalyst system of claim 1 wherein the first modifier is selected fromthe group consisting of tris(pentafluorophenyl)borane, dimethylaniliniumtetra(pentafluorophenyl)borate, dimethylaniliniumtetra(pentafluorophenyl)-aluminate, dimethylaniliniumtetrafluoroaluminate, tri(n-butyl)ammonium)tetra(pentafluorophenyl)borate, tri(n-butyl)ammonium)tetra(pentafluorophenyl)-aluminate, tri(n-butyl)ammonium)tetrafluoroaluminate, the sodium, potassium, lithium, tropyliun and thetriphenylearbenium salts of these compounds, and combinations thereof.8. The catalyst system of claim 1 wherein the second modifier isselected from the group consisting of unsubstituted and substitutedcyclopentadienes, indenes, fluorenes, fulvenes, and combinationsthereof.
 9. The catalyst system of claim 1 wherein the second modifieris selected from the group consisting of cyclopentadiene,methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene,hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene,1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene,1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene,4-methyl-1-indene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene,fluorene, methylfluorene, cycloheptatriene, methylcycloheptatriene,cyclooctatraene, methylcyclooctatraene, fulvene and dimethylfulvene.bis-indenylethane, bis(4,5,6,7-tetrahydro-1-indenyl)ethane,1,3-propanedinyl-bis(4,5,6,7-tetrahydro)indene, propylene-bis(1-indene),isopropyl(1-indenyl) cyclopentadiene, diphenylmethylene(9-fluorenyl),cyclopentadiene, isopropylcyclopentadienyl-1-fluorene and combinationsthereof.
 10. The catalyst system of claim 1, wherein said secondmodifier is a 1,3-diene.
 11. The catalyst system of claim 1, whereinsaid second modifier is indene.
 12. The catalyst system of claim 1wherein the molar ratio of the first modifier to the metal contained inthe bulky ligand metallocene catalyst compound is about 0.01 to 100 13.The catalyst system of claim 1 wherein the molar ratio of the firstmodifier to the metal contained in the bulky ligand metallocene catalystcompound is about 0.01 to
 10. 14. The catalyst system of claim 1 whereinthe molar ratio of the second modifier to the metal contained in thebulky ligand metallocene catalyst compound is about 0.01 to 100
 15. Thecatalyst system of claim 1 wherein the molar ratio of the secondmodifier to the metal contained in the bulky ligand metallocene catalystcompound is about 0.01 to
 10. 16. The catalyst system of claim 1 whereinthe bulky ligand metallocene catalyst compound is represented by LMX_(n)wherein: M is a metal atom from Groups 3 to 15 or the Lanthanide seriesof the Periodic Table of Elements; L is a substituted or unsubstituted,π-bonded bulky ligand coordinated to M, each X is independently selectedfrom the group consisting of hydrogen, an aryl, alkyl, alkenyl,alkylaryl, or arylalkyl radical having 1 to 20 carbon atoms, ahydrocarboboxy radical having 1 to 20 carbon atoms, a halide, and anitrogen containing radical having 1 to 20 carbon atoms; and wherein nis 2, 3 or 4 depending on the valence of M.
 17. The catalyst system ofclaim 1, wherein the bulky ligand metallocene catalyst compound isrepresented by either:

wherein: M is a metal atom from Groups 3 to 15 or the Lanthanide seriesof the Periodic Table of Elements; L is a substituted or unsubstituted,π-bonded bulky ligand coordinated to M Each Q can be the same ordifferent and is independently selected from the group consisting of—O—, —NR—, —CR₂- and —S—; Y is C or S; Z is selected from the groupconsisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, and substituted orunsubstituted aryl group with the proviso that when Q is —NR— then Z isselected from the group consisting of —OR, —NR₂, —SR, —SiR₃, —PR₂ and—H; n is 1 or 2; A is a univalent anionic group when n is 2 or A is adivalent anionic group when n is 1; when n is 2, A can be the groupformed by QQYZ depicted in formula I above; and R can be the same ordifferent and is independently a group containing carbon, silicon,nitrogen, oxygen, and/or phosphorus wherein one or more R groups may beattached to the L substituent; or

wherein: M is a metal atom from Groups 3 to 15 or the Lanthanide seriesof the Periodic Table of Elements; L is a substituted or unsubstituted,π-bonded ligand coordinated to M; Q can be the same or different and isindependently selected from the group consisting of —O—, —NR—, —CR₂— and—S— Y is either C or S; Z is selected from the group consisting of —OR,—NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, and substituted or unsubstituted arylgroup with the proviso that when Q is —NR— then Z is selected from thegroup consisting of —OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; n is 1 or 2; Ais a univalent anionic group when n is 2 or A is a divalent anionicgroup when n is 1; when n is 2, A can be the group formed by QQYZdepicted in formula II above; R can be the same or different and isindependently a group containing carbon, silicon, nitrogen, oxygen,and/or phosphorus wherein one or more R groups may be attached to the Lsubstituent; T is a bridging group selected from the group consisting ofan alkylene or arylene group containing from 1 to 10 carbon atomsoptionally substituted with carbon or heteroatoms, germaniun, siliconeand alkyl phosphine; and m is 1 to
 7. 18. The catalyst system of claim 1wherein the catalyst system further comprises an activator compoundselected from the group consisting of methylalumoxane, modifiedmethylalumoxane and combinations thereof.
 19. The catalyst system ofclaim 1, wherein the bulky ligand metallocene catalyst is selected fromthe group consisting of a mono-cyclopentadienyl zirconiumtriscarboxylate, a mono-cyclopentadienyl zirconium trispivalate,1,3-dimethylcyclopentadienylzirconium and wherein the catalyst systemhas an activity at least 400% greater than the activity of a differentcatalyst system comprising the same bulky ligand metallocene catalystwith no modifier.